7519-94-0Relevant articles and documents
4-bromophenylboronate derivatives of ring and cage borosilicates
Avent, Anthony G.,Lawrence, Simon E.,Meehan, Margaret M.,Russell, Tom G.,Spalding, Trevor R.
, p. 1051 - 1060 (2002)
The reactions between equimolecular amounts of 4-bromophenylboronic acid and di-tertbutylsilanediol or tert-butylsilanetriol in toluene solutions at reflux temperatures afforded the borosilicate ring compound [(4-BrC6H4B)O2/sub
Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Bartholomeyzik, Teresa,Pendrill, Robert,Lihammar, Richard,Jiang, Tuo,Widmalm, G?ran,B?ckvall, Jan-E.
supporting information, p. 298 - 309 (2018/01/17)
Pd-catalyzed C-C bond-forming reactions under oxidative conditions constitute a class of important and widely used synthetic protocols. This Article describes a mechanistic investigation of the arylating carbocyclization of allenynes using boronic acids and focuses on the correlation between reaction conditions and product selectivity. Isotope effects confirm that either allenic or propargylic C-H activation occurs directly after substrate binding. With an excess of H2O, a triene product is selectively formed via allenic C-H activation. The latter C-H activation was found to be turnover-limiting and the reaction zeroth order in reactants as well as the oxidant. A dominant feature is continuous catalyst activation, which was shown to occur even in the absence of substrate. Smaller amounts of H2O lead to mixtures of triene and vinylallene products, where the latter is formed via propargylic C-H activation. The formation of triene occurs only in the presence of ArB(OH)2. Vinylallene, on the other hand, was shown to be formed by consumption of (ArBO)3 as a first-order reactant. Conditions with sub-stoichiometric BF3·OEt2 gave selectively the vinylallene product, and the reaction is first order in PhB(OH)2. Both C-H activation and transmetalation influence the reaction rate. However, with electron-deficient ArB(OH)2, C-H activation is turnover-limiting. It was difficult to establish the order of transmetalation vs C-H activation with certainty, but the results suggest that BF3·OEt2 promotes an early transmetalation. The catalytically active species were found to be dependent on the reaction conditions, and H2O is a crucial parameter in the control of selectivity.
Unveiling the role of boroxines in metal-free carbon-carbon homologations using diazo compounds and boronic acids
Bomio, Claudio,Kabeshov, Mikhail A.,Lit, Arthur R.,Lau, Shing-Hing,Ehlert, Janna,Battilocchio, Claudio,Ley, Steven V.
, p. 6071 - 6075 (2017/08/29)
By means of computational and experimental mechanistic studies the fundamental role of boroxines in the reaction between diazo compounds and boronic acids was elucidated. Consequently, a selective metal-free carbon-carbon homologation of aryl and vinyl boroxines using TMSCHN2, giving access to TMS-pinacol boronic ester products, was developed.
